US9920515B2 - Thermoplastic polyolefin membrane with enhanced thermal resistance - Google Patents

Thermoplastic polyolefin membrane with enhanced thermal resistance Download PDF

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Publication number
US9920515B2
US9920515B2 US13/701,770 US201113701770A US9920515B2 US 9920515 B2 US9920515 B2 US 9920515B2 US 201113701770 A US201113701770 A US 201113701770A US 9920515 B2 US9920515 B2 US 9920515B2
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thermoplastic polyolefin
weight percent
stabilizer
titanium dioxide
package
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US20130130581A1 (en
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Linlin Xing
Thomas J. Taylor
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BMIC LLC
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Building Materials Investment Corp
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Priority claimed from PCT/US2011/047039 external-priority patent/WO2012021489A1/en
Publication of US20130130581A1 publication Critical patent/US20130130581A1/en
Assigned to BUILDING MATERIALS INVESTMENT CORPORATION reassignment BUILDING MATERIALS INVESTMENT CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TAYLOR, THOMAS J., XING, LINLIN
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Assigned to BMIC LLC reassignment BMIC LLC CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: BUILDING MATERIALS INVESTMENT CORPORATION
Assigned to DEUTSCHE BANK AG NEW YORK BRANCH reassignment DEUTSCHE BANK AG NEW YORK BRANCH SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BMIC LLC, ELK COMPOSITE BUILDING PRODUCTS, INC., ELK PREMIUM BUILDING PRODUCTS, INC., ELKCORP, GAF Energy LLC, HBP ACQUISITION LLC, SIPLAST, INC., SPECIALTY GRANULES INVESTMENTS LLC
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    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E04B1/7608—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only comprising a prefabricated insulating layer, disposed between two other layers or panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/028—Net structure, e.g. spaced apart filaments bonded at the crossing points
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
    • E04D5/06—Roof covering by making use of flexible material, e.g. supplied in roll form by making use of plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B32B2419/06—Roofs, roof membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]

Definitions

  • This invention relates generally to roofing products, and more particularly to roofing membranes and geomembranes formulated to have enhanced thermal resistance.
  • TPO Thermoplastic polyolefin based roofing membranes are one of many types of roofing membranes available on the market today.
  • TPO may be a melt blend or reactor blend of a polyolefin plastic, such as a polypropylene polymer, with an olefin copolymer elastomer (OCE), such as an ethylene-3Q propylene rubber (EPR) or an ethylene-propylene-diene rubber (EPDR).
  • OCE olefin copolymer elastomer
  • EPR ethylene-3Q propylene rubber
  • EPDR ethylene-propylene-diene rubber
  • Examples of commercially available TPO membranes include SURE WELDTM (Carlisle Inc.), GENFLEXTM (Omnova Solutions, Inc), ULTRAPLYTM (Firestone Building Products) and EVERGUARD TPOTM (OAF). Novel stretchable TPO membranes are disclosed in U.S. Pat. No. 7,666,491, which is incorporated by reference
  • TPO based membranes may also be used as geomembranes to cover landfills, storage ponds of water, and the like.
  • Such TPO membranes may have a higher polypropylene content than a similar TPO roofing membrane and sometimes they are referred to as fPP (flexible polypropylene) membranes or sheets.
  • TPO-based roofing membranes may comprise one or more layers.
  • a TPO membrane may comprise base-(bottom) and cap-(top) layers with a fiber reinforcement scrim (middle) sandwiched between the other two layers.
  • the scrim may be a woven, nonwoven, or knitted fabric composed of continuous strands of material used for reinforcing or strengthening membranes. The scrim is generally the strongest layer in the composite.
  • the fabric can contribute significantly to the tensile strength of the roofing membrane and provide for dimensional stability.
  • the fabric reinforcement comprises a polyester yarn based scrim. Glass fiber based scrims may also be used for situations where additional weight and/or improved dimensional stability are desired.
  • thermoplastic polyolefin composition may include a thermoplastic polyolefin resin and a UV stabilizer package comprising 0.001 weight percent to 3 weight percent ultrafine titanium dioxide.
  • the UV stabilizer package may comprise from 0.5 weight percent to 2 weight percent ultrafine titanium dioxide.
  • the UV stabilizer package may comprise from 1.5 weight percent to 2 weight percent ultrafine titanium dioxide.
  • a thermoplastic polyolefin roofing membrane may comprise a cap layer made of a first thermoplastic polyolefin composition, the first thermoplastic polyolefin composition comprising thermoplastic polyolefin resins and a UV stabilizer package.
  • the disclosed roofing membrane may also include a core layer made of a second thermoplastic polyolefin composition and a scrim layer disposed between the cap layer and the core layer.
  • the UV stabilizer package of the first thermoplastic polyolefin composition comprises from 0.001 weight percent to 3 weight percent ultrafine titanium dioxide.
  • a method of manufacturing a thermoplastic polyolefin membrane may include providing a first thermoplastic polyolefin mixture comprising a thermoplastic polyolefin resin and a UV stabilizing package comprising 0.001 weight percent to 3 weight percent ultrafine titanium dioxide.
  • the disclose method may further include extruding a first thermoplastic polyolefin layer from the first thermoplastic polyolefin mixture.
  • FIG. 1 illustrates a perspective, side view of an exemplary TPO membrane in accordance with the present disclosure.
  • FIG. 1 is a perspective, side view of a portion TPO membrane 100 .
  • the TPO membrane 100 comprises a cap layer 102 and a core layer 104 .
  • a scrim layer 106 is substantially sandwiched between the cap layer 102 and the core layer 104 .
  • Each of the cap layer 102 and core layer 104 is made of a TPO sheet.
  • the TPO membrane 100 When installed on the roof of a house, the TPO membrane 100 may be oriented such that the cap layer 102 is facing upward toward the direction of sunlight and the core layer 104 is facing downward toward the roof.
  • the cap layer 102 may be formulated with additives such as UV stabilizers, UV absorbers, antioxidants, process and thermal stabilizers, fire retardants, white pigments or color pigments, and any other additives known in the art.
  • the formulation of the cap layer 102 may provide for long-term stability in an outside environment and provide an aesthetic appearance if containing color pigments. While the core layer 104 may be formulated to include additives, the core layer 104 may be configured to include no additives to reduce costs. In embodiments in which the core layer 104 includes additives, the formulation for the core layer 104 may be the same as the formulation for the cap layer 102 . In another embodiment in which the core layer 104 includes additives, the formulation for the core layer 104 may be different from the formulation for the cap layer 102 .
  • a method of preparing TPO membrane 100 may comprise first mixing the additives with TPO to effect a desired formulation and forming a sheet of TPO by extrusion. As such, the additives may be distributed throughout the TPO sheet.
  • scrim 106 may be disposed between the TPO sheets 102 and 104 , and the three layers may be laminated together at an elevated temperature such that the two TPO layers 102 and 104 are fused and welded together through the interstices of the scrim 106 .
  • Solar panels may be rigid solar panels as well as flexible solar panels.
  • Flexible solar panels may be installed on the roof by directly laminating the backside of the solar panels to the top side of roofing membranes.
  • a significant amount of heat may be generated by the solar panels, especially if they have dark colors.
  • the heat in turn may be transferred to the surface of roofing membranes that are underneath of the flexible solar panels. Consequently, the surface temperature of roofing membranes underneath the solar panels can reach over 200 F in hot climates.
  • geomembranes may have flexible solar panels laminated or otherwise attached to their cap layers.
  • a flexible solar panel (not shown) may be laminated to the cap layer 102 of the TPO membrane 100 .
  • the cap layer 102 may be subject to the heat generated by the solar panel.
  • the absorption of intense light during the summer can also subject the TPO membrane 100 to a high temperature.
  • TPO roofing membranes are designed to withstanding field temperature below 180 F. If TPO roofing membranes are exposed to a field temperature higher than 180 F for an extended period (such as a couple of years), the TPO membranes may degrade quickly due to UV radiation along with thermal-oxidative degradation caused by high-temperature exposure. Such degradation may lead to surface cracking of the TPO membranes and therefore premature field failure or roof leaking.
  • the cap layer 102 and core layer 104 of the TPO membrane 100 may be formulated to include TPO resins.
  • Additives may be included in the TPO cap layer 102 to enhance the resistance to degradation.
  • additives may also be included in the TPO core layer 104 .
  • Suitable additives may include a UV stabilizer package.
  • a UV stabilizer package may include any combination of one or more below ingredients: 1) UV stabilizers functioning as free radical scavengers (e.g., Tinuvin XT-850, which is a Hindered Amine Light Stabilizer (“HALS”)); 2) antioxidants functioning as inhibitors of thermo-oxidative degradation at a broad temperature range for long-term thermal stabilizers (e.g., Irganox 1010, which is a sterically hindered phenolic antioxidant); 3) process or thermal stabilizers functioning as inhibitors of thermo-oxidative degradation during extrusion process (e.g., Irgastab FS301, which is a system comprised of a phosphate processing stabilizer Irgafos 168 and a high molecular weight hydroxylamine Irgastab FS042); and/or 4) UV absorber functioning to absorb UV light and dissipate it as thermal energy (e.g., Tinuvin 328, which is 2-(2H-benzotriazol-2-yl
  • the TPO cap layer 102 and/or core layer 104 may further include other additives.
  • the formulation for TPO cap layer 102 and/or core layer 104 may include rutile titanium dioxide (TiO 2 ) and at least one fire retardant.
  • the formulation for TPO cap layer 102 may include 1-10 weight percent rutile TiO 2 .
  • the formulation for TPO cap layer 102 may include 2-4 weight percent rutile TiO 2 .
  • TiO 2 may also be included in a UV stabilizer/antioxidant package as described in U.S. Patent Pub. No. 2004/0157075, which is incorporated by reference herein.
  • rutile TiO 2 and ultrafine TiO 2 , such as the DuPontTM Light Stabilizer 210 (“DLS 210”), which in some embodiment may have a mean particle size of 130 nm.
  • rutile TiO 2 generally has a mean particle size ranging from around 250 nm or more.
  • an exemplary heat-resistant TPO formulation comprises TPO resins and a UV stabilizer package that includes 0.001 to 3 weight percent ultrafine TiO 2 .
  • the exemplary heat-resistant TPO formulation may further comprise rutile TiO 2 and a fire retardant.
  • the UV stabilizer package in the heat resistant formulation may include any suitable components described in the present disclosure.
  • the UV stabilizer package may include Tinuvin XT-850, Tinuvin 328, Irgastab FS301.
  • UV stabilizer package may include Tinuvin XT-850, Tinuvin 328, Uvasorb HA88FD (a HALS), Irgastab FS301, and Irganox 1010. It is to be appreciated that various combinations of UV stabilizer packages components in various amounts may be used together with ultrafine TiO 2 to provide various heat-resistant TPO formulations in accordance with the principles of the present disclosure.
  • the heat-resistant formulation 1 includes a UV stabilizer package comprising 2% DLS 210, along with 1.7% Tinuvin XT-850, 0.5% Tinuvin 328, and 0.5% Irgastab FS301.
  • the UV stabilizer package in comparative example A includes only 2% DLS 210 without additional additives.
  • the UV stabilizer package in comparative example B does not include any ultrafine TiO 2 but is otherwise the same.
  • the UV stabilizer package in comparative example C does not include any ultrafine TiO 2 but includes an additional 0.25% of Irganox 1010.
  • test TPO membranes were tested according to the 280 F oven test method, which comprises the following steps: 1) set the oven temperature to 280 F for a forced air oven which is well calibrated; 2) put 1 by 2.75 inch piece of the test TPO membrane into the oven; 3) after oven aging for a time period, take the sample out of the oven to cool it down to room temperature; 4) wrap the sample around 3 inch mandrel to examine the TPO cap layer side to see if there are visible cracks under 10 ⁇ magnification; and 5) if there is visible cracks under 10 ⁇ magnification, record numbers of days the TPO sample being aged inside of 280 F oven.
  • an exemplary heat-resistant formulation comprises TPO resins and a UV stabilizer package that includes 0.25-2 weight percent ultrafine TiO 2 .
  • an exemplary heat-resistant formulation comprises TPO resins and a UV stabilizer package that includes 0.5-2 weight percent ultrafine TiO 2 .
  • an exemplary heat-resistant formulation comprises TPO resins and a UV stabilizer package that includes 1.5-2 weight percent ultrafine TiO 2 .
  • Table 2 Shown in Table 2 is the correlation between the amount of ultrafine TiO 2 and the corresponding effectiveness in resisting heat-induced degradation.
  • Exemplary heat-resistant formulations 2-5 are identical except the amount of ultrafine TiO 2 (DLS210) is increased from 0.5% to 2%. The days it took for cracks to develop did not increase linearly with increases in the concentration of ultrafine TiO 2 . While each formulation still provides improved heat resistance over comparative examples D and E, there appears to be an optimal heat resistance at around 1.5% to 2% ultrafine TiO 2 .
  • ultrafine TiO 2 may vary as the composition of the UV stabilizer package varies. It is to be further appreciated that the optimal concentration of ultrafine TiO 2 may vary as the mean particle size of the ultrafine TiO 2 varies.
  • Ultrafine TiO 2 suitable for the formulations of the present disclosure may have a mean particle size of 165 nm or less. In an embodiment, ultrafine TiO 2 having a mean particle size between 125 to 150 nm may be used. In another embodiment, ultrafine TiO 2 having a mean particle size between 110 to 165 nm may be used. It is to be appreciated that the embodiments provide herein are merely exemplary, and may be adjusted in accordance with the principles of the present disclosure.
  • the cap layer 102 may be formulated according to any of the heat-resistant TPO formulations disclosed in the present disclosure.
  • the entirety of the cap layer 102 may formulated with the heat-resistant TPO formulation of the present disclosure.
  • only a portion of the cap layer 102 is formulated with the heat-resistant TPO formulation of the present disclosure.
  • the cap layer 102 may include a first sub-layer (not shown) adjacent to the outer surface of the cap layer 102 , and in an embodiment, the cap layer 102 may be configured to have the first sub-layer formulated with the heat-resistant TPO formulation of the present disclosure.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Physics & Mathematics (AREA)
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  • Structural Engineering (AREA)
  • Acoustics & Sound (AREA)
  • Electromagnetism (AREA)
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US13/701,770 2010-08-09 2011-08-09 Thermoplastic polyolefin membrane with enhanced thermal resistance Active US9920515B2 (en)

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US11309828B2 (en) 2019-11-27 2022-04-19 GAF Energy LLC Roof integrated photovoltaic module with spacer
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US11394344B2 (en) 2020-08-11 2022-07-19 GAF Energy LLC Roof mounted photovoltaic system and method for wireless transfer of electrical energy
US11398795B2 (en) 2019-12-20 2022-07-26 GAF Energy LLC Roof integrated photovoltaic system
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US20230222889A1 (en) * 2020-10-01 2023-07-13 Bmic Llc Roofing shingle having uniquely identifiable radio frequency-based tag and methods of use thereof
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US9045904B2 (en) * 2012-11-16 2015-06-02 Firestone Building Products Co., LLC Thermoplastic membranes containing expandable graphite
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